Method for preparation of carborane anions

ABSTRACT

This invention relates to an improved method for making unsubstituted carborane anions and monosubstituted carborane anions of formula: (R—CB n —H m′ ) −  where n is an integer ranging from 5 to about 11 and m′ is an integer ranging from 5 to 16 where the relative values of n and m′ depend upon the exact structure of the carborane and the presence of a non-hydrogen substituent. m as used herein is an integer ranging from 5 to 16. When R is hydrogen the anion is unsubstituted. When R is a halogen, a phenyl, a substituted phenyl group, such as fluorophenyl group, or any other substituent, the carborane is substituted. The method is particularly useful for preparation of twelve-vertex carborane anions R—CB 11 H 11   − , where R is a defined above, and is specifically useful for preparation of the unsubstituted carborane CB 11 H 12 -??, where R is H.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the National Stage of International Application No. PCT/US02/10060, filed Apr. 1, 2002, which claims the benefit of U.S. provisional application Ser. No. 60/280,243, filed Mar. 30, 2001, which is hereby incorporated by reference to the extent not inconsistent herewith.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with U.S. Government support under National Science Foundation Grant No. 981979. The Government has certain rights in this invention.

BACKGROUND OF THE INVENTION

It is generally known that salts of the twelve-vertex carborane anion CB₁₁H₁₂ ⁻(I) serve as starting materials for the preparation of partially and fully substituted anions of the type CB₁₁X_(n)H_((12−n)) ⁻ (II, where the substituents X need not be the same). The latter are of considerable interest as relatively inert and weakly nucleophilic anions for applications including, among others, incorporation in catalysts for olefin polymerization, incorporation in lithium cation battery electrolytes, and incorporation in radioactive waste treatment materials. The most common choices of substituent X for such applications are X=halogen, X=alkyl, and X=halogenated alkyl, e.g. trifluoromethyl.

Carborane anions, such as II, are described in U.S. Pat. No. 5,731,470, which is incorporated by reference in its entirety herein. This patent describes synthesis of these anions (II) from the corresponding unsubstituted anion (I). The patent also discusses the use of carborane anions in batteries and electrochromic displays.

Until the present time, the high cost of the starting material, CB₁₁H₁₂ ⁻, has discouraged commercial use of these highly promising anions. As far as we are aware, this starting material is at present sold commercially by only one company (Katchem Ltd., Prague, Czech Republic), and is very expensive. Currently the anion is produced from an expensive precursor, decaborane, in three steps; the synthesis is difficult to scale up and is performed in small batches.

The present invention provides a method for making unsubstituted anions (I) and related unsubstituted and monosubstituted carborane anions at significantly lower cost. The new synthetic method provided makes the use of these anions, and substituted anions, such as II, practical for commercial applications.

SUMMARY OF THE INVENTION

This invention relates to an improved method for making unsubstituted carborane anions and monosubstituted carborane anions of formula: (R—CB_(n)—H_(m′))⁻ where n is an integer ranging from 5 to about 11 and m′ is an integer ranging from 5 to 16 where the relative values of n and m′ depend upon the exact structure of the carborane and the presence of a non-hydrogen substituent. m as used herein is an integer ranging from 5 to 16. When R is hydrogen the anion is unsubstituted. When R is a halogen, a phenyl, a substituted phenyl group, such as a fluorophenyl group, or any other substituent, the carborane is substituted. The method is particularly useful for preparation of twelve-vertex carborane anions R—CB₁₁H₁₁ ⁻, where R is as defined above, and is specifically useful for preparation of the unsubstituted carborane CB₁₁H₁₂—, where R is H.

The synthetic method involves reaction of a borane anion B_(n)H_(m) ⁻ with a carbene (Y¹Y²C:) preferably, but not necessarily, in the presence of a strong base. Although not wishing to be bound by any particular mechanism, it is believed that the carbene inserts into a borane dianion B_(n)H_(m′−1) ²⁻ which is generated from the starting borane monoanion by the action of strong base. The strong base can serve a dual function, in that it can also be instrumental in the generation of the carbene (Y¹Y²C:). Exemplary strong bases useful in this reaction include hydride, e.g., provided as NaH, or organolithium compounds (e.g., including alkyl or aromatic lithium compounds), such as n-butyllithium.

A salt of the starting borane anion (B_(n)H_(m))⁻M⁺ is dissolved or partially dissolved in an appropriate solvent, preferably an ether. The choice of cation employed depends at least in part on the solvent employed and is compatible with the reagents used as discussed below. When desired, strong base is added to the reaction mixture at this point. A carbene Y¹Y²C: where one or both of Y¹ and Y² can be a halide or another substituent such as a phenyl group or a substituted phenyl group is generated and inserts into the borane cage giving the carborane anion to generate CB_(n)H_(m′) ⁻, (where R is H) particularly when both Y¹ and Y² are both chlorides and a strong base was present, and R—CB_(n)H_(m′) ⁻ when other choices of Y¹ and Y² are made (for example, when one or both of Y¹ and Y² are R) or when strong base was absent. Depending on the nature of the substituent R, it resides either in position 1 of the carborane cage of the product, i.e., on the carbon atom (e.g., when R is phenyl), or in position 2, i.e., on a boron that is located next to the carbon atom (e.g., when R is bromine).

Carbenes useful in the reactions of this invention can be generated by a variety of methods that are well known in the art. Dichlorocarbene is of particular use in the synthesis of CB₁₁H₁₂ ⁻. Dichlorocarbene is generated for example, in chloroform by the action of strong base, as is well known in the art. Halocarbenes and dihalocarbenes are generally preferred for use in these syntheses.

A preferred base is NaH combined with a small amount of an alcohol such as methanol or ethanol, which is converted into a well soluble sodium alkoxide, assuring smooth dichlorocarbene formation from chloroform. A small amount of a side product R—CB_(n)H_(m′) ⁻ in which R is alkoxy, located in position 2, is then also formed, but can be removed easily because its salts are quite soluble in water. When nitrogen bases, includes amines, are present in the carbene insertion reaction mixtures, they have a much stronger tendency to appear as substituents in the carborane anion products. Nitrogen bases are, thus, not suitable for use as strong bases in the reactions of this invention unless a nitrogen-containing substituent is desired (e.g., in the CB₁₁H₁₂ ⁻ product, this substituent will appear in position 2). It is often desirable to handle the starting borane anions in the form of salts with certain alkylamines that have good solubility in solvents, such as tetrahydrofuran (THF) and dimethyl ether (DME), employed in the reactions of this invention. The cations of nitrogen bases can be used in the starting borane salts of this invention, particularly those of nitrogen bases that are volatile, however, care must be taken to convert the starting borane into a salt with another cation such as Na⁺ first and to substantially remove any nitrogen base thus avoiding its presence in the carbene insertion reaction mixture to avoid undesirable substitution.

Solvents for the reaction and the addition of cations to the reaction mixture are selected to avoid premature precipitation of borane anions or borane dianions and decreased yields of desired products For example, it is believed that no reaction of B₁₁H₁₄ ⁻ was observed when 1,4-dioxane was used as the solvent because the disodium salt of B₁₁H₁₃ ²⁻ is barely soluble in this solvent.

The carborane anion products are isolated from the reaction mixture as salts R—CB_(n)H_(m′) ⁻M⁺. Preferred cations M⁺ are alkylammonium cations, such as trialkyl ammonium cations which are added after completion of the reaction.

In a specific embodiment, the methods of this invention are employed in the synthesis of the carborane CB₁₁H₁₂ ⁻. Salts of this twelve-vertex carborane anion can be prepared in about 40% yield from inexpensive and readily available materials in a single step. The procedure can be completed in one day and can be readily scaled up. The presently preferred synthetic reaction involves an insertion of dichlorocarbene into the eleven-vertex borane anion B₁₁H₁₄ ⁻ (presumably, as discussed above, in the form of the dianion, B₁₁H₁₃ ²⁻, produced in the presence of a strong base). The sodium salt of B₁₁H₁₄ ⁻ is a preferred starting material, however, this salt can be difficult to handle and when dry, ignites spontaneously in air. The sodium salt of B₁₁H₁₄ ⁻ can be formed in situ by initial addition of a soluble salt in which the cation is a cation of a volatile base, such as an alkylamine, followed by removal of the volatile base under reduced pressure. A preferred cation for the preparation of these salts in situ is the trimethylammomium cation. This is also the preferred cation for isolation of the salt of the product from the reaction mixture.

In a preferred embodiment, the product salt (CB₁₁H₁₂)⁻(CH₃)₃NH⁺ is formed in high purity, about 98%. The only detectable impurity (2%) in the isolated product is the 2-chloro derivative of the desired product, 2-Cl—CB₁₁H₁₁ ⁻ (where substituents are numbered as is conventional in the art). For most intended applications the product salt can be employed without further purification. Art-known methods, such as preparative HPLC or exploitation of differential solubility (the trimethylammonium salt of the 2-chloro substituted anion is more soluble in water than the parent anion), can be employed for further purification if desired.

In yet other specific embodiments, carbenes other than dichlorocarbene can be used to generate the unsubstituted anion or its variously substituted derivatives such as 1-R—CB₁₁H₁₁ ⁻, where R, for example, is a phenyl group or a substituted phenyl group.

Salts of the starting borane anion, B₁₁H₁₄ ⁻, are well-known and readily synthesized by known methods. The trimethylammonium salt can be readily synthesized in one step from inexpensive commercially available precursors, sodium borohydride (NaBH₄) and boron trifluoride (BF₃).

Other borane anions can also be used and provide access to additional carborane anions, such as CB₉H₁₂ ⁻. The method of synthesis of this invention, thus is not limited to a single carbene and single borane anion, and is general.

The invention is further illustrated by the following non-limiting examples.

DETAILED DESCRIPTION OF THE INVENTION

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻: from [Me₃NH]⁺[B₁₁H₁₄]⁻; CCl₂ from CHCl₃/NaH+EtOH, medium scale. In a 2 L two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻[1] (20 g, 0.104 mol) was dissolved in THF (200 mL) under an argon atmosphere. The solution was cooled to 0° C. and NaH (95%) (23 g, 1 mol) was added carefully. After stirring 30 min at room temperature, the THF and NMe₃ were removed in vacuum and THF (400 mL) and CHCl₃ (30 ml, 0.375 mol) were added. The reaction mixture was stirred for 2 h at ambient temperature. EtOH (80 ml) were added dropwise at 0° C. and it was stirred for 4 h at room temperature. Water (600 mL) was added and the THF was removed in vacuum and the solution was acidified by addition of 10% HCl. Residual THF and EtOH were removed in vacuum. [Me₃NH]⁺Cl⁻(20 g, 0.2 mol) was added, and a white solid precipitated, which was dried in vacuum to yield a colorless mixture of [Me₃NH]⁺[CB₁₁H₁₂]⁻(8.9 g, 42%) containing 2% of a [Me₃NH]⁺[2-Cl-1-CB₁₁H₁₂]⁻ contaminant as judged by ¹¹B NMR.

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻: CCl₂ from CHCl₃/NaH+EtOH. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₂]⁻(1 g, 5.2 mmol) was dissolved in THF (10 mL) under an argon atmosphere. The solution was cooled to 0° C. and NaH (95%) (1.0 g, 44 mmol) was added carefully. After stirring 15 min at room temperature, the THF and NMe₃ were removed under reduced pressure and THF (20 mL) and CHCl₃ (1.5 ml, 18.8 mmol) were added. The reaction mixture was stirred briefly (up to 1 h; this makes no difference) at ambient temperature. EtOH (4mL) was added dropwise at 0° C. and the mixture was stirred for 2 h at room temperature.

H₂O (30 mL) was added, the THF and EtOH were removed under reduced pressure and the solution was acidified by addition of 10% HCl. [Me₃NH]⁺Cl⁻(1 g, 10 mmol) was added, and a white solid precipitated, which was dried under reduced pressure to yield colorless [Me₃NH]⁺[CB₁₁H₁₂]⁻(445 mg, 42%); by ¹¹B NMR analysis, this contains a 2% impurity of [Me₃NH]⁺[2-Cl-1-CB₁₁H₁₂].

[Me₄NH]⁺Cl⁻(0.5 g, 4.6 mmol) was added to the filtrate, and a white precipitate was separated and dried under reduced pressure. The residue was dissolved in methanol (6 mL) and filtered. The filtrate was injected on a HPLC and a 50/50 MeOH/H₂O mixture was used to separate [2-(EtO)-1-CB₁₁H₁₁]⁻(R_(F)=16.7). Methanol was removed from the eluate under reduced pressure and the residual aqueous solution was extracted three times with diethyl ether (40 mL). The combined ether extracts were evaporated to dryness and the colorless oil was dissolved in water (50 mL). After addition of a solution of [Me₃NH]⁺Cl⁻(0.5 g, 4.6 mmol) in H₂O (20 mL), the white precipitate was filtered and dried under reduced pressure to yield [Me₄N]⁺[2-EtO-1-CB₁₁H₁₂]⁻(67 mg, 5%).

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻: CCl₂ from EtOH/NaH+CHCl₃. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻[1](1 g, 5.2 mmol) was dissolved in THF (10 mL) under an argon atmosphere. The solution is cooled to 0° C. and NaH (95%) (1.0 g, 44 mmol) was added carefully. After stirring 15 min at room temperature, the THF and NMe₃ were removed in vacuum and THF (20 mL) was added. EtOH (1 mL, 16 mmol) and afterwards CHCl₃ (1.5 ml, 18.8 mmol) were added dropwise at 0° C. The reaction mixture was stirred for 1 h at ambient temperature.

EtOH (3 ml) and H₂O (30 mL) were added, the THF and EtOH were removed in vacuum and the solution was acidified by addition of 10% HCl. [Me₃NH]⁺Cl⁻(1 g, 10 mmol) was added, and a white solid precipitated, which was dried in vacuum to yield colorless [Me₃NH]⁺[CB₁₁H₁₂]⁻(445 mg, 42%) containing a 2% impurity of [Me₃NH]⁺[2-Cl-1-CB₁₁H₁₂]⁻ as judged by ¹¹B NMR.

The addition of the CHCl₃ in the last two experiments was conducted at different temperatures (−30° C., 0° C., 67° C.). It was shown that the yields were not improved by using different temperatures.

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻: CCl₂ from EtOH/NaH+CHCl₃. In a 250 mL three-neck flask Me₃NH⁺B₁₁H₁₄ ⁻(5.0 g, 0.026 mol) was dissolved in THF (50 mL) under an argon atmosphere. After cooling to 0° C. NaH (95%, 2.00 g, 0.088 mol) was added slowly. After warming up to room temperature stirring was continued for 30 min. The mixture was evaporated to dryness under reduced pressure and THF (100 mL) was added. The resulting mixture was cooled to 0° C. and NaOEt (4.42 g, 0.0650 mol) was added. Over a period of 2.5 h CHCl₃ (3.1 mL, 0.039 mol) was added. The reaction mixture was allowed to warm to room temperature over a period of 18 h. The solvent was evaporated and water (100 mL) was added. The solution was acidified by the addition of 10% HCl (20 mL). Residual THF and EtOH were removed under reduced pressure. Charcoal (1 g) was added to the solution and stirred for 5 min., then the solid material was filtered off. After addition of Me₃NHCl (5 g, 0.05 mol) to the filtrate a white solid (3.19 g) precipitated. The solid was then dissolved in 2 N NaOH (50 mL) and stirred for 2 h. The basic layer was extracted with Et₂O (3×30 mL) and the solvent removed under reduced pressure. The resulting oil was dissolved in water (30 mL) and Me₃NHCl (5 g. 0.05 mol) was added. The compound was purified by column chromatography on silica gel (180 g, column 3.5×20 cm, CH₂Cl₂/MeCN=4: 1, R_(f)=0.31) to yield Me₃NH⁺CB₁₁H₁₂ ⁻(1.63 g, 30%).

Synthesis of [NMe₃H]⁺[CB₁₁H₁₂]⁻: CCl₂ from EtONa/NaH+CHCl₃. In a 500 mL three-neck flask Me₃NH⁺B₁₁H₁₄ ⁻(5 g, 26 mmol) was dissolved in THF (100 mL) under argon atmosphere. The solution was cooled to 0° C. and NaH (95%, 1.45 g, 60 mmol) was added slowly. After stirring for 30 min at 0° C. the cooling was removed and the mixture was evaporated to dryness under reduced pressure and THF (150 mL) was added. NaOEt (6.80 g, 100 mmol) was added to the reaction flask and the mixture was again cooled to 0° C. CHCl₃ (5.20 mL, 70 mmol) was added over a period of 11 h. The reaction mixture was stirred for 1 h at 0° C. and then slowly warmed to room temperature. Water (100 mL) was added and THF was evaporated under reduced pressure. The solution was acidified by the addition 10% HCl (40 mL). Residual THF and EtOH were removed under reduced pressure. Charcoal (2 g) was added and the solution was stirred for an additional 15 minutes at which time the solid material was filtered off. Upon the addition of Me₃NHCl to the supernatant (5 g, 50 mmol) a white solid precipitated. The solid was dried under reduced pressure to yield a mixture of [Me₃NH]⁺[CB₁₁H₁₂]⁻ and [Me₃NH]⁺[CB₁₁H₁₁OEt]⁻(2.40 g), with a ratio of products of approximately 3:1, respectively. A small amount of Me₃NH⁺B₁₁H₁₄ (<5%) was also present in the isolated material. The material was dissolved in methanol (20 mL) and water (50 mL) was added. The solution was boiled until its volume was 35–40 mL and allowed to cool slowly to room temperature and then placed in the refrigerator overnight. A white solid crystallized. The solution was filtered and NMe₃H⁺CB₁₁H₁₂ ⁻(0.770 g, 4 mmol, ˜92% purity) was collected. The supernatant was again heated to boiling and the volume reduced to 30–35 mL. The solution was allowed to cool to room temperature and placed in the refrigerator for several h. Upon cooling a solid crystallized from the solution. Filtration yielded [Me₃NH]⁺[CB₁₁H₁₁OEt]⁻(0.300 g, 1 mmol, ˜85% purity).

The NMe₃H⁺CB₁₁H₁₂ ⁻ product (0.770 g, 4 mmol) was added to a 50 mL saturated aqueous solution of CsOH and allowed to stir for 3 h after which time the solid in the solution was collected by filtration. The filtrate was washed with acetone and again the solids were filtered. Evaporation of the acetone yielded Cs⁺CB₁₁H₁₂ ⁻(0.350 g, 1 mmol, ˜95% pure). The material insoluble in the acetone was dissolved in HCl (10%, 10 mL) and upon the addition of Me₃NHCl (0.100 g, 1 mmol) a solid precipitate formed. The solid collected was Me₃NH⁺B₁₁H₁₄ ⁻(0.090 g 0.4 mmol). The CsOH solution was extracted with ether/acetone (70/30, 3×75 mL) to yield additional Cs⁺CB₁₁H₁₂ ⁻(0.200 g, 0.7 mol, ˜98–99% pure).

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻: CCl₂ from CHCl₃/NaH+MeOH. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻[1](1 g, 5.2 mmol) was dissolved in THF (10 mL) under an argon atmosphere. The solution was cooled to 0° C. and NaH (95%) (1.0 g, 44 mmol) was added carefully. After stirring 15 min at room temperature, the THF and NMe₃ were removed in vacuum and THF (20 mL) and CHCl₃ (1.5 mL, 18.8 mmol) were added. The reaction mixture was stirred briefly (up to 1 hr; this makes no difference) 1 h at ambient temperature. MeOH (4 mL) was added dropwise at 0° C. and the stirring was continued for 2 h at room temperature.

H₂O (30 mL) was added, the THF and MeOH were removed under reduced pressure and the solution was acidified by addition of 10% HCl. [Me₃NH]⁺Cl⁻ (1 g, 10 mmol) was added, and a white solid precipitated, which was dried under reduced pressure to yield colorless [Me₃NH]⁺[CB₁₁H₁₂]³¹ (445 mg, 42%); by ¹¹B NMR analysis, this contains a 2% impurity of [Me₃NH]⁺[2-Cl-1-CB₁₁H₁₂]⁻.

[Me₄N]⁺Cl⁻ (0.5 g, 4.6 mmol) was added to the filtrate, and a white precipitate was separated and dried under reduced pressure. The residue was dissolved in methanol (6 mL) and filtered. The filtrate was injected on an HPLC and a 50/50 MeOH/H₂O mixture was used to separate [2-MeO-1-CB₁₁H₁₁]⁻ (R_(F)=16.7). Methanol was removed from the eluate under reduced pressure and the residual aqueous solution was extracted three times with diethyl ether (40 mL). The combined ether extracts were evaporated to dryness and the colorless oil was dissolved in water (50 mL). After addition of a solution of [Me₄H]⁺[Cl]⁻ (0.5 g, 4.6 mmol) in H₂O (20 mL), the white precipitate was filtered and dried under reduced pressure to yield [Me₄N]⁺[2-(MeO)-1-CB₁₁H₁₂]⁻ (64 mg, 5%). Another byproduct, [Me₄N]⁺[2-CCl₂H—CB₁₁H₁₁]⁻ is also formed (2%).

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻: CCl₂ from CHCl₃+NaOH. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻[1] (1 g, 5.2 mmol) was dissolved in H₂O (20 mL) with NaOH (0.5 g, 12.5 mmol) under an atmosphere of argon. After stirring 1 h at room temperature, the H₂O was removed in vacuum and THF (20 mL) was added. The reaction mixture was cooled to −78° C. and CHCl₃ (2 mL, 24 mmol) was added. The reaction mixture was allowed to stir over night at ambient temperature.

The THF was removed in vacuum and the residue was taken up in 50 mL of water, and the solution was acidified by addition of 10% HCl. After addition of [Me₃NH]⁺Cl⁻ (1 g, 10 mmol) a white solid precipitated, which yielded after drying in vacuum a colorless mixture of [Me₃NH]⁺[CB₁₁H_(12]) ⁻ (270 mg, 22%), [Me₃NH]⁺[B₁₁H₁₄]⁻(370 mg, 37%), and [Me₃NH]⁺[2-Cl-1-CB₁₁H₁₂]⁻ (75 mg, 5%), as judged by ¹¹B NMR.

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻: CCl₂ from CHCl₃+BuLi, neat NaB₁₁H₁₄. In a 250 mL two-neck flask [Na]⁺[B₁₁H₁₄]⁻ [1] (1 g, 6.4 mmol) was dissolved in THF (20 mL) under an argon atmosphere. The solution was cooled to −78° C. and n-BuLi (7.5 mL, 12 mmol) was added dropwise. After stirring 1 h at room temperature the solution was cooled to −78° C. and CHCl₃ (2 mL, 24 mmol) was added, and the reaction mixture was allowed to stir over night at ambient temperature.

The THF was removed in vacuum and the residue was taken up in 50 mL of water. The solution was acidified by addition of 10% HCl and after addition of [Me₃NH]+Cl⁻ (1 g, 10 mmol) a white solid precipitated, which was dried under reduced pressure to yield a colorless mixture of [Me₃NH]⁺[CB₁₁H₁₂]⁻ ⁽280 mg, 22%) and [Me₃NH]⁺[2-Cl-1-CB₁₁H₁₂]⁻ (75 mg, 5%) as judged by ¹¹B NMR. It can be difficult to isolate and handle the dry sodium salt of [B₁₁H₁₄]⁻. Na[B₁₁H₁₄] forms solvates with solvents, and in its dry form it spontaneously ignites in air. K[B₁₁H₁₄]⁻ and Me₄N[B₁₁H₁₄]⁻ salts have very limited solubility in solvents like THF, and therefore they are not very useful for these reactions.

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂: CCl₂ from CHCl₃+BuLi, NaB₁₁H₁₄ made in situ. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻[1](1 g, 5.2 mmol) was dissolved in THF (20 mL) under an argon atmosphere. The solution was cooled to −78° C. and n-BuLi (4 mL, 6.4 mmol) was added dropwise. After stirring 1 h at room temperature the solvent was removed in vacuum and THF (20 mL) was added. The solution was cooled to −78° C. and (8 mL, 12.8 mmol) n-BuLi was added. After stirring 1 h at room temperature the solution was cooled to −78° C. and CHCl₃ (2 ml, 24 mmol) were added. The reaction mixture was allowed to stir overnight at ambient temperature. The THF was removed in vacuum and the residue was taken up in 50 mL of H₂O. The solution was acidified by addition of 10% HCl. After addition of [Me₃NH]⁺Cl⁻(] g, 10 mmol) a white solid precipitated, which was dried in vacuum to yield a colorless mixture of [Me₃NH]⁺[CB₁₁H₁₂]⁻(290 mg, 27%) and [Me₃NH]⁺[B₁₁H₁₄]⁻ (320 mg, 32%), as judged by ¹¹B NMR.

The Use of Different Strong Bases:

Other bases such as NaOMe, NaOEt, NaOBu¹, NaOH, amyl sodium were used in addition to NaH and BuLi. The yields of isolated [Me₃NH]⁺[CB₁₁H₁₂]⁻ with these other bases were around 10% and by far not as good as with NaH.

The use of Solvents Other than THF:

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻ DME as solvent. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻[1] (1 g, 5.2 mmol) was dissolved in DME (10 mL) under an argon atmosphere. The solution was cooled to 0° C. and NaH (95%) (1.0 g, 44 mmol) was added carefully. After stirring 15 min at room temperature, the THF and NMe₃ were removed in vacuum and DME (20 mL) and CHCl₃ (1.5 ml, 18.8 mmol) were added. The reaction mixture was stirred for 1 h at ambient temperature. EtOH (4 mL) was added dropwise at 0° C. and it was stirred for 2 h at room temperature.

H₂O (30 mL) was added, the DME and EtOH were removed in vacuum and the solution was acidified by addition of 10% HCl. [Me₃NH]⁺Cl⁻ (1 g, 10 mmol) was added, and a white solid precipitated, which was dried under reduced pressure to yield a colorless mixture of [Me₃NH]⁺[CB₁₁H₁₂]⁻ (425 mg 38%) containing [Me₃NH]⁺[2-Cl-1-CB₁₁H_(12]) ⁻ as a 2% impurity, as judged by ¹¹B NMR.

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻: diglyme as solvent. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻[1] (1 g, 5.2 mmol) was dissolved in diglyme (10 mL) under an argon atmosphere. The solution was cooled to 0° C. and NaH (95%) (1.0 g, 44 mmol) was added carefully. After stirring 15 min at room temperature, the THF and NMe₃ were removed in vacuum, and diglyme (20 mL) and CHCl₃ (1.5 ml, 18.8 mmol) were added. The reaction mixture was stirred for 1 h at ambient temperature. EtOH (4 mL) was added dropwise at 0° C. and it was stirred for 2 h at room temperature. H₂O (30 mL) was added, the diglyme and the EtOH were removed in vacuum and the solution was acidified by addition of 10% HCl. [Me₃NH]⁺Cl⁻ (1 g, 10 mmol) was added, and a white solid precipitated, which was dried under reduced pressure to yield a colorless mixture of [Me₃NH]⁺[CB₁₁H₁₂]⁻ (200 mg, 19%) and colorless [Me₃NH]⁺[2-Cl-1-CB₁₁H₁₂]⁻ (37 mg, 3%), as judged by ¹¹B NMR. When 1,4 dioxane was used under the conditions as described for diglyme, only unreacted [Me₃NH]⁺[B₁₁H₁₄]⁻ was obtained, because the Na₂[B₁₁H₁₃] is barely soluble in 1,4 dioxane.

Synthesis of [Me₃NH]⁺[2-Cl-1-CB₁₁H₁₂]⁻: CCl₂ from PhHgCCl₃ (note: no base present; it appears from this experiment that the presence of a base is essential to avoid 2-substitution). Into a 25 mL two-neck flask with [Me₃NH]⁺[B₁₁H₁₄]⁻(100 mg, 0.5 mmol), and PhHgCCl₃ (2 g, 5 mmol) diglyme (5 mL) was added, and the mixture was heated overnight at 130° C. under an argon atmosphere. After cooling down to room temperature, the diglyme solution was transferred to a separation funnel and H₂O (25 mL) was added. The water layer was extracted three times with diethyl ether (25 mL) and the ether layers were separate and combined. The ether was removed in vacuum and the diglyme was removed in a Kugelrohr. The residue was dissolved in methanol (3 mL) and filtered. The filtrate was injected on a HPLC and a 50/50 MeOH/H₂O mixture was used to separate unreacted starting material [B₁₁H₁₄]⁻(R_(F)=13) (49 mg, 49%) from [2-Cl-1-CB₁₁H₁₁]⁻(R_(F)=17.5).

The methanol was removed in vacuum from the combined MeOH/H₂O/[2-Cl-1-CB₁₁H₁₁]⁻ fraction. The aqueous solution was extracted three times with diethyl ether (20 mL) and the organic layers were separated from the aqueous layer. The combined ether extracts were evaporated to dryness and the colorless oil was dissolved in water (40 mL). After addition of [Me₄N]⁺[Cl]⁻ (0.1 g, 1 mmol) in H₂O (20 mL), the white pure [Me₄N]⁺[2-Cl-1-CB₁₁H₁₁]⁻ was filtered and dried in vacuum to yield (20 mg, 20%). When corrected for the recovered starting material, the yield of the 2-chloro derivative is 40%.

Synthesis of [2-Me₃N-1-CB₁₁H₁₂]⁻: CCl₂ from CHCl₃+n-BuLi and neat [Me₃NH]⁺[B₁₁H₁₄]⁻ (note: in the presence of amine nucleophiles, position 2 is substituted). In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻[1] (1 g, 5.2 mmol) was dissolved in THF (20 mL) under an argon atmosphere. The solution was cooled to −78° C. and n-BuLi (10 mL, 16 mmol) was added dropwise. After stirring 1 h at room temperature, the solution was cooled to −78° C. and CHCl₃ (2 mL, 24 mmol) was added, and the reaction mixture was allowed to stir over night at room temperature.

The THF was removed in vacuum and the residue was taken up in 50 ml of water, and the solution was acidified by addition of 10% HCl. A yellow solid was filtered and washed three times with 10 mL portions of water and dried in vacuum to yield pale yellow [2-Me₃N-1-CB₁₁H₁₂] (200 mg, 19%). [Me₃NH]⁺Cl⁻ (1 g, 10 mmol) was added to the filtrate, a white solid was filtered, washed three times with 10 mL portions of water and dried in vacuum to recover colorless starting material [Me₃NH]⁺[B₁₁H₁₄]⁻ (300 mg, 30%).

It appears very important to substantially remove trimethylamine from the reaction mixture under reduced pressure if unsubstituted product is to be made. Most of the nitrogen bases attack and substitute the 2-position of [CB₁₁H₁₂]⁻. Therefore all nitrogen containing bases were excluded in the investigations.

Separation of [Me₃NH]⁺[CB₁₁H₁₂]⁻ from [B₁₁H₁₄]⁻ (in case of incomplete carbene insertion reaction). In a 250 mL flask with 2N NaOH (50 mL) a mixture of [Me₃NH]⁺[B₁₁H₁₄]⁻ (400 mg, 2.1 mmol) and [Me₃NH]⁺[CB₁₁H₁₂]⁻ (600 mg, 2.9 mmol) were added and stirred for 1 h at room temperature. The Me₃N was removed in vacuum and the strong alkaline solution was extracted three times with diethylether (30 mL). The ether from the combined ether extracts was removed in vacuum and the oil was dissolved in H₂O (50 mL). The solution was acidified by addition of 10% HCl and after addition of [Me₃NH]⁺Cl⁻ (0.5 g, 5 mmol) a white solid precipitated, which was filtered and dried in vacuum to yield pure colorless [Me₃NH]⁺[CB₁₁H₁₂]⁻ (570 mg, 95%).

The use of other carbenes besides CCl₂:

Synthesis of [Me₄N]⁺[CB₁₁H₁₁]⁻ and [Me₄N]⁺[2-Br-1-CB₁₁H₁₁]⁻: CBr₂ from CHBr₃+NaOEt/NaH⁻ (CBr₂ inserts but over half of the product contains a bromine substituent in position 2). In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻ (1 g, 5.2 mmol) was dissolved in dry THF (20 mL) under an argon atmosphere. The solution was cooled to 0° C., and NaH (95%) (1.2 g, 53 mmol) was added. After stirring 15 min at room temperature, the THF and the Me₃N was removed in vacuum. THF (40 mL) was added to the residue, the suspension was cooled to 0° C., and CHBr₃ (2 mL, 22.9 mmol) was added.

The reaction mixture was stirred over night at room temperature. Ethanol (10 mL) was added slowly to the mixture. After addition of water (20 mL), the THF and the ethanol were removed in vacuum and 1N NaOH (100 mL) was added. The solution was transferred to a separation funnel, and the alkaline solution was extracted three times with diethyl ether (25 mL) and the ether layers were separated from the aqueous layer. The combined ether extracts were evaporated to dryness and the pale yellow oil was dissolved in methanol (5 mL) and filtered. The filtrate was injected on a HPLC and a 53/47 MeOH/H₂O mixture was used to separate the desired [CB₁₁H₁₂]⁻(R_(F)=15) from the byproduct [2-Br-1-CB₁₁H ₁₁]⁻(R_(F)=23).

The methanol was removed under reduced pressure from the combined MeOH/H₂O fractions containing [CB₁₁H₁₂]⁻ and the aqueous solution was extracted three times with diethyl ether (40 mL). The combined ether extracts were evaporated to dryness and the colorless oil was dissolved in water (50 mL). After addition of a solution of [Me₄N]⁺[Cl]⁻ ⁽0.5 g, 4.6 mmol) in H₂O (20 mL), the white [Me₄N]⁺[CB₁₁H₁₂]⁻ was filtered and dried in vacuum to yield (0.15 g, 14%).

The methanol was removed under reduced pressure from the combined MeOH/H₂O fractions containing [2-Br-1-CB₁₁H₁₁]⁻ and the aqueous solution was extracted three times with diethyl ether (40 mL). The combined ether extracts were evaporated to dryness and the colorless oil was dissolved in water (50 mL). After addition of a solution of [Me₄N]⁺[Cl]⁻ (0.5 g, 4.6 mmol) in H₂O (20 mL), the white pure [Me₄N]⁺[2-Br-1-CB₁₁H₁₁]⁻ was filtered and dried in vacuum to yield (0.3 g, 19%).

Attempted Synthesis of [CB₁₁H₁₂]⁻ using CI₂ produced [Me₄N]⁺[7-OH—B₁₁H₁₃]⁻: CI₂ from CHI₃+NaH (CHI 3 acted as an oxidizing agent and no CI₂ insertion was observed). In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻ (1 g, 5.2 mmol) was dissolved in THF (20 mL) under an argon atmosphere. The solution was cooled to −78° C., and NaH (95%) (0.9 g, 40 mmol) was added. After stirring 15 min at room temperature, the THF and the Me₃N was removed in vacuum. THF (40 mL) was added to the residue and the suspension was cooled to −78° C., and CHI₃ (6 g, 15.3 mmol) was added.

The reaction mixture was stirred over night at room temperature. Ethanol (10 mL) and water (50 mL) were added, the THF and the ethanol were removed in vacuum. The solution was acidified by addition of 10% HCl. After filtration [Me₄N]⁺[Cl]⁻ (0.57 g, 5.2 mmol) in H₂O (20 mL) was added to the filtrate and the white precipitate was filtered and dried in vacuum. The residue was crystallized from CH₃CN/H₂O, to yield colorless crystals of [Me₄N]⁺[7-OH—B₁₁H₁₃]⁻ (290 mg, 25%).

Synthesis of [Me₄N]⁺[4-R—C₆H₄-1-CB₁₁H₁₁]⁻(R═H, F): PhCCl from PhCHCl₂. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻ (1 g, 5.2 mmol) was dissolved in dry THF (10 mL) under an argon atmosphere. The solution was cooled to 0° C., and NaH (95%) (1.2 g, 53 mmol) was added. After stirring 15 min at room temperature, the THF and the Me₃N were removed in vacuum. THF (20 mL) was added to the residue and the suspension was cooled to 0° C., and a mixture of (4-R—C₆H₄-CHCl₂) (2 mL, 15.3 mmol, R═H) (2 mL, 14.9 mmol, R═F) and ethanol (1.5 mL) was added slowly.

The reaction mixture was stirred overnight at room temperature, and EtOH (3 mL) was added slowly. After addition of water (50 mL), the THF and the EtOH were removed in vacuum and the solution was transferred to a separation funnel where residual (4-R—C₆H₄-CHCl₂) (R═H,F) was separated from the aqueous layer. [Me₃NH]⁺Cl⁻ (1 g, 10 mmol) was added to the water layer, and a white precipitate was separated and dried under reduced pressure. The residue was dissolved in methanol (6 mL) and filtered. The filtrate was injected on a HPLC column and a 58/42 MeOH/H₂O mixture was used to elute the [4-R—C₆H₄-1-CB₁₁H₁₁]⁻ (R═H, R_(F)=21.5; R═F, R_(F)=28.3) product.

Methanol was removed under reduced pressure, the aqueous solution was extracted three times with diethyl ether (40 mL), the combined ether extracts were evaporated to dryness and the colorless oil was dissolved in water (50 mL). After addition of a solution of [Me₄N]⁺[Cl]⁻ (0.5 g, 4.6 mmol) in H₂O (20 mL), the white precipitate was filtered and dried under reduced pressure to yield pure [Me₄N]⁺[4-R—C₆H₄-1-CB₁₁H₁₂]⁻ (R═H, F) (293 mg, 19%, R═H; 330 mg, 18%, R═F).

Synthesis of [NMe₄]⁺[(4-C₆H₅—C₆H₄)-1-CB₁₁H₁₁]⁻. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻ (1 g, 5.2 mmol) was dissolved in dry THF (10 mL) under an argon atmosphere. The solution was cooled to 0° C., and NaH (95%) (1.5 g, 66 mmol) was added carefully. After stirring 15 min at room temperature, THF and NMe₃ were removed under reduced pressure. THF (20 mL) was added to the residue and the suspension was cooled to 0° C., and a mixture of p-C₆H₅—C₆H₄CHCl₂ (2.37 g, 10.0 mmol) and ethanol (2.0 mL) was added slowly. The reaction mixture was stirred overnight at room temperature, and EtOH (3 mL) was added slowly. After addition of water (50 mL), THF and the EtOH were removed under reduced pressure and the solution was transferred to a separation funnel where residual p-C₆H₅—C₆H₄CHCl₂ was separated from the aqueous layer. [Me₄N]⁺[Cl]⁻ (1 g, 9.2 mmol) was added to the water layer, and a white precipitate was separated and dried under reduced pressure to yield [NMe₄]⁺[closo-1-(p-C₆H₅—C₆H₄)—CB₁₁H₁₁]⁻ (537 mg, 28%). MS (z/e): 295. NMR: ¹¹B {¹H}: −7.6 (12), −12.9 (2–11); ¹H: 7.60–7.22 (m) Ph.

Synthesis of [NMe₄]⁺[(4-Br—C₆H₄)-1-CB₁₁H₁₁]⁻. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻ (1 g, 5.2 mmol) was dissolved in dry THF (10 mL) under an argon atmosphere. The solution was cooled to 0° C., and NaH (95%) (1.5 g, 66 mmol) was added carefully. After stirring 15 min at room temperature, THF and NMe₃ were removed under reduced pressure. THF (20 mL) was added to the residue and the suspension was cooled to 0° C., and a mixture of p-Br—C₆H₄CHCl₂ (2.40 g, 10.0 mmol) and ethanol (2.0 mL) was added slowly. The reaction mixture was stirred overnight at room temperature, and EtOH (3 mL) was added slowly. After addition of water (50 mL), THF and the EtOH were removed under reduced pressure and the solution was transferred to a separation funnel where residual p-BrC₆H₄CHCl₂ was separated from the aqueous layer. [Me₄N]⁺[Cl]⁻ (1 g, 9.2 mmol) was added to the water layer, and a white precipitate was separated and dried under reduced pressure to yield [NMe₄]⁺[closo-1-(p-Br—C₆H₄)—CB₁₁H₁₁]⁻ (369 mg, 19%). NMR: ¹¹B{¹H}: −8.1 (12), −13.1 (2–11); ¹H: 7.21–6.97 (m) Ph.

Synthesis of [PPh₄]⁺[(4-I—C₆H₄)-1-CB₁₁H₁₁]⁻. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻ (1 g, 5.2 mmol) was dissolved in dry THF (10 mL) under an argon atmosphere. The solution was cooled to 0° C., and NaH (95%) (1.5 g, 66 mmol) was added carefully. After stirring 15 min at room temperature, THF and NMe₃ were removed under reduced pressure. THF (20 mL) was added to the residue and the suspension was cooled to 0° C., and a mixture of p-I—C₆H₄CHCl₂ (2.87 g, 10.0 mmol) and ethanol (2.0 mL) was added slowly. The reaction mixture was stirred overnight at room temperature, and EtOH (3 mL) was added slowly. After addition of water (50 mL), THF and the EtOH were removed under reduced pressure and the solution was transferred to a separation funnel where residual p-IC₆H₄CHCl₂ was separated from the aqueous layer. [Me₄N]⁺[Cl]⁻ (1 g, 9.2 mmol) was added to the water layer, and a white precipitate was separated and dried under reduced pressure. A small amount (157 mg) of the residue was dissolved in methanol (4 mL) and filtered. The filtrate was injected on a HPLC column and a 60/40 MeOH/H₂O mixture was used to elute the [closo-1-(p-IC₆H₄)—CB₁₁H₁₁]⁻(R_(F)=17.2) product. Methanol was removed under reduced pressure, the aqueous solution was extracted three times with diethyl ether (15 mL), the combined ether extracts were evaporated to dryness, and the colorless oil was dissolved in water (15 mL). After addition of a solution of [PPh₄]⁺[Cl]⁻ (375 mg, 1 mmol), the white precipitate was filtered and dried under reduced pressure to yield pure [PPh₄]⁺[closo-1-(p-IC₆H₄)—CB¹¹H₁₁]⁻ (21 mg, 3%). NMR: ¹¹B {¹H}: −7.5 (12), −12.8 (2–11); ¹H: 7.49–7.26 (m) Ph.

Synthesis of [Me₄N]⁺[7-OH—B₁₁H₁₃]⁻. When the synthesis of [1-Ph-CB¹¹H¹¹]⁻: PhCCl from PhCCl₃ was attempted [Me₄N]⁺[7-OH—B₁₁H₁₃]³¹ was formed since E PhCCl₃ acted as an oxidizing agent and not as a carbene generating agent. In a 250 mL two-neck flask [Me₃NH]⁺[B₁₁H₁₄]⁻[1] (1 g, 5.2 mmol) was dissolved in THF (20 mL) under an argon atmosphere. The solution was cooled to −78° C. and n-BuLi (10 ML, 16 mmol) was added dropwise. After stirring 1 h at room temperature, the solution was cooled to −78° C. and C₆H₅CCl₃ (1 mL, 7 mmol) was added, and the reaction mixture was heated overnight under reflux. After cooling to room temperature, the THF was removed in vacuum and the residue was taken up in 25 mL of water, and the solution was acidified by addition of 10% HCl. [Me₄N]⁺ Cl⁻ (1 g, 9.1 mmol) was added and a white solid precipitated. The solid was filtered and dried in vacuum to yield colorless [Me₄N]⁺[7-OH—B₁₁H₁₃]⁻ (250 mg, 22%).

The use of Other Starting Boranes in Addition to [B₁₁H₁₄]⁻:

We have observed carbon insertion into B₁₀H₁₄ and into its degradation product, [B₉H₁₄]⁻. These experiments are only preliminary; yields and selectivity of product formation can be improved with methods known in the art.

Synthesis of [Me₄N]⁺[nido-1-Cl-1-CB₉H₁₂]⁻ and [Me₄N]⁺[closo-1-CB₁₀H₁₁]⁻: CCl₂ from CHCl₃+NaOEt/NaH with B₁₀H₁₄ (under the reaction condition B₁₀H₁₄ partly degraded to [B₉H₁₄]⁻; carbene insertion occurred into B₁₀H₁₄ to give [closo-1-CB₁₀H₁₁]⁻ and into [B₉H₁₄]⁻ to give [nido-1-Cl-1-CB₉H₁₂]⁻; modification of reaction conditions will allow selectivity). In a 250 mL two-neck flask B₁₀H₁₄ (611 mg, 5 mmol) was dissolved in THF (40 mL) and NaH (95%) (1.2 g, 53 mmol) was added at 0° C. After stirring 15 min at room temperature, the mixture was cooled to 0° C. and CHCl₃ (2 mL, 24 mmol) was added. After stirring for 1 h at room temperature, EtOH (3 mL) was added dropwise and the stirring was continued for another 2 h. After addition of water (50 mL), the THF and EtOH were removed in vacuum, the solution was acidified with 10% HCl, and a white solid precipitated by addition of [Me₄N]⁺Cl⁻ (1 g, 9.1 mmol) and dried in vacuum to yield a colorless mixture of [Me₄N]⁺[B₉H₁₄]⁻ (343 mg, 40%), [Me₄N]⁺[nido-1-Cl-1-CB₉H₁₂]⁻ (172 mg, 15%) and [Me₄N]⁺[closo-1-CB₁₀H₁₁]⁻ (110 mg, 11%), as determined by ¹¹B NMR.

The residue was dissolved in methanol (6 mL) and filtered. The filtrate was injected on an HPLC and a 48/52 MeOH/H₂O mixture was used to separate the [nido-1-Cl-1-CB₉H₁₂]⁻ (R_(F)=29.5) and the [closo-1-CB₁₀H₁₁]^(− (R) _(F)=17.9) carborane products from the borane [Me₄N]⁺[B₉H₁₄]⁻.

Methanol was removed under reduced pressure from the [nido-1-Cl-1-CB₉H₁₂]⁻ fraction, the residual aqueous solution was extracted three times with diethyl ether (40 mL) and the organic layers were separated from the aqueous layer. The combined ether extracts were evaporated to dryness and the colorless oil was dissolved in water (50 mL). After addition of a solution of [Me₄N]⁺[Cl]⁻ (0.5 g, 4.6 mmol) in H₂O (20 mL), the white pure [Me₄N]⁺[nido-Cl-1-CB₉H₁₂]⁻ was filtered and dried under reduced pressure (127 mg, 11%).

Methanol was removed under reduced pressure from the [closo-1-CB₁₀H₁₁]⁻ fraction, the aqueous solution was extracted three times with diethyl ether (40 mL), the combined ether extracts were evaporated to dryness and the colorless oil was dissolved in water (50 mL). After addition of a solution of [Me₄N]⁺[Cl]⁻ (0.5 g, 4.6 mmol) in H₂O (20 mL), the white pure [Me₄N]⁺[closo-1-CB₁₀H₁₁]⁻ was filtered and dried under reduced pressure (80 mg, 8%).

Synthesis of [Me₃NH]⁺[nido-1-(4-F-C₆H₄)-1-CB₉H₁₂]⁻: 4-F—C₆H₄-CCl from 4F—CH₆H₄—CHCl₂+NaOEt/NaH with B₁₀H₁₄ (note: the base degraded B₁₀H₁₄ to [B₉H₁₄]⁻, which then reacted with the carbene; much of it was left over; conditions could clearly be improved by one of ordinary skill in the art—after a complete conversion of B₁₀H₁₄ to [B₉H₁₄]⁻ the carbene can be added in quite good yield). In a 250 mL two neck flask B₁₀H₁₄ (611 mg, 5 mmol) was dissolved in THF (40 mL) and at 0° C. NaH (95%) (1.2 g, 53 mmol) was added. After stirring 15 min at room temperature, the mixture was cooled at 0° C. and a mixture of 4-F—C₆H₄—CHCl₂ (2 mL, 14.9 mmol) and EtOH (1.9 mL) was added dropwise. After stirring for 1 h at room temperature, EtOH (3 mL) was added dropwise and the mixture was stirred for another 2 h. After addition of water (50 mL) the THF and EtOH were removed under reduced pressure, the solution was acidified with 10% HCl, and [Me₄N]⁺Cl⁻ (1 g, 9.1 mmol) was added. A white solid precipitated and was dried in vacuum to yield a colorless mixture of [Me₄N]⁺[B₉H₁₄]⁻ (343 mg, 40%), and [Me₄N]⁺[nido-1-(4-F—C₆H₄)-1-CB₉H₁₂] (190 mg, 13%, as determined by ¹¹B NMR analysis).

The residue was dissolved in methanol (6 mL) and filtered. The filtrate was injected on an HPLC column and a 58/42 MeOH/H₂O mixture was used to separate [nido-1-(4-F—C₆H₄)-1-CB₉H₁₂]⁻(R_(F)=34.1) from [B₉H₁₄]⁻ (R_(F)=29.8). Methanol was removed under reduced pressure from the [nido-1-(4-F—C₆H₄)-1-CB₉H₁₂]⁻ fraction, the aqueous solution was extracted three times with diethyl ether (40 mL). The combined ether extracts were evaporated to dryness and the colorless oil was dissolved in water (50 mL). After addition of a solution of [Me₄N]⁺[Cl]⁻ (0.5 g, 4.6 mmol) in H₂O (20 mL), the white pure [Me₄N]⁺[nido-1-(4-F—C₆H₄)-1-CB₉H₁₂]⁻ was filtered and dried in vacuum to yield (145 mg, 10%).

Attempted insertion of CCl₂ into B₁₀H₁₄: CCl₂ from CHCl₃+NaOH with B₁₀H₁₄ (resulted in formation of [Me₃BH]⁺[B₉H₁₄]⁻ by degradation of B₁₀H₁₄).

In a 250 mL two neck flask B₁₀H₁₄ (611 mg, 5 mmol) was dissolved in 2N NaOH (50 mL) and after addition of CHCl₃ (3 mL, 36 mmol) the reaction mixture was stirred over night at room temperature.

The solution was acidified by addition of 10% HCl and after addition of [Me₃NH]⁺Cl⁻ (1 g, 10 mmol) a pale yellow solid precipitated and dried in vacuum to yield colorless [Me₃NH]⁺[B₉H₁₄]⁻ (670 mg, 78%).

Below, the chemical equations for the new synthesis of CB₁₁H₁₂ ⁻ from B₁₁H₁₄ ⁻ and its old synthesis from B₁₀H₁₄ are summarized.

Synthesis of [Me₃NH]⁺[CB₁₁H₁₂]⁻. In a 500 mL three-neck flask Me₃NH⁺B₁₁H₁₄ ⁻ (5 g, 0.026 mol) was dissolved in THF (50 mL) under argon atmosphere. The solution was cooled to 0° C. and NaH (95%, 2.61 g, 0.10 moles) was added slowly. After stirring for 30 min at 0° C. the cooling was removed and the mixture was evaporated to dryness under reduced pressure and THF (120 mL) was added. NaOEt (8.80 g, 0.13 moles) was added to the reaction flask and the mixture was again cooled to 0° C. CHCl₃ (6.20 mL, 0.08 mol) was added over a period of 5 h. The reaction mixture was stirred for 8 h at 0° C. Water (100 mL) was added and THF was evaporated under reduced pressure. The solution was acidified by the addition 10% HCl (40 mL). Residual THF and EtOH were removed under reduced pressure. Charcoal (2 g) was added to the solution and the solid material was filtered off. Upon the addition of Me₃NHCl to the supernatant (5 g, 0.05 mol) a white solid precipitated. The solid was dried under reduced pressure to yield Me₃NH⁺CB₁₁H₁₂ ⁻ (2.20g, 41%) of approximately 93% purity.

Although the description above contains many specificities, these are intended as illustrations of the presently—preferred embodiments of the invention, not as limitations. All references cited herein are hereby incorporated by reference to the extent not inconsistent with the disclosure herewith.

REFERENCES

-   (1) Dunks, G. B.; and Ordonez, K. P.; Inorg. Chem., 1978, 17, 1514. -   (2) Ple{hacek over (s)}ek, J.; Jelínek, T.; Drdáková, E.; He{hacek     over (r)}mánek, S. and {hacek over (S)}tíbr, B.; Collect. Czech.     Chem. Commun., 1984, 49 1559. -   (3) Knoth, W. H.; Little, J. L.; Lawrence, J. R.; Scholer, F. R. and     Todd, L. J.; Inorg.

Synth., 1968, 11, 33. 

1. A method for making a carborane anion of formula R—CB_(n)H_(m′)— where R is H, a halide, a phenyl group or a substituted phenyl group, n is an integer ranging from (5–11) which comprises the step of reacting a substituted carbene of formula: Y¹Y²C: where Y¹ and Y² can be any of H, a halide, a phenyl group or substituted phenyl group with a borane anion of formula: B_(n)H_(m)—, in the presence of a strong base, wherein n, m and m′ are integers, n ranging from 5 to 11 and m and m′ ranging from 5 to 16 and wherein the relative values of n, m and m′ depend upon the exact structure of the borane starting material.
 2. The method of claim 1 wherein the strong base is hydride.
 3. The method of claim 1 wherein the strong base is an alkyllithium compound.
 4. The method of claim 1 wherein the strong base is not a nitrogen base.
 5. The method of claim 1 wherein the carbene is dihalocarbene and R is H.
 6. The method of claim 5 wherein the carbene is dichlorocarbene.
 7. The method of claim 1 wherein the borane anion is provided as an Na⁺ salt.
 8. The method of claim 1 wherein the borane anion is provided as an ammonium salt.
 9. The method of claim 8 wherein any amine generated during reaction is substantially removed.
 10. The method of claim 1 wherein the borane anion is at least partially solubilized in solvent.
 11. The method of claim 1 wherein the solvent is TBF, DME or diglyme.
 12. The method of claim 1 wherein the carbene is PhY²C: where Y² is a halide and the carborane anion formed is Ph-CB_(n)H_(n) ⁻ where Ph is a phenyl or a substituted phenyl group.
 13. The method of claim 1 wherein the carborane is CB₁₁H₁₂ ⁻.
 14. The method of claim 1 wherein the carborane is R—CB₁₁H₁₂ ⁻ and R is not hydrogen.
 15. The method of claim 13 wherein the carbene is PhY²C: Y² is a halide and the carborane is Ph-CB₁₁H₁₂ ⁻ where Ph is a phenyl group or a substituted phenyl group.
 16. A method for making the carborane anion CB_(n)H_(m′) which comprises reacting the anion B_(n)H_(m′−1) ²⁻ with a carbene.
 17. The method of claim 16 wherein the carborane anion is CB₁₁H₁₂ ⁻ and the carbene is a dihalocarbene.
 18. A method for making the carborane anion CB₁₁H₁₂ ⁻ which comprises the steps of: reacting a borane anion of formula B₁₁H₁₄ ⁻ with a carbene of formula Y¹Y²C:, where Y¹ and Y² can be any of H, a halide, a phenyl group or substituted phenyl group, in the presence of a strong base.
 19. The method of claim 18 wherein the strong base is an alkyllithium compound.
 20. The method of claim 18 wherein the carbene is a dihalocarbene.
 21. The method of claim 18 wherein the carbene is dichlorocarbene.
 22. A method for making the carborane anion CB₁₁H₁₂ ⁻ which comprises the step of providing a solution containing the borane anion B₁₁H₁₄ ⁻ and a strong base, generating a carbene of formula Y¹Y²C:, where Y¹ and Y² can be any of H, a halide, a phenyl or a substituted phenyl group, in the solution to react to form the carborane anion.
 23. The method of claim 22 further comprising isolating the carborane anion as a salt.
 24. The method of claim 23 wherein the carborane anion is isolated by precipitation of a carborane anion salt from solutions.
 25. The method of claim 24 wherein the carborane anion salt is an ammonium salt.
 26. The method of claim 18 wherein the strong base is hydride. 